Amines derived from THPE

ABSTRACT

Amines endowed with chain extension activity for formulations such as polyureas are disclosed, which have the general formula: ##STR1## wherein n is 0-1000; R 1  =R 2 , and R 1  and R 2  are from the group --CH 2  --CH 2  --; --CH 2  --C(CH 3 )H--; and --C(CH 3 )H--CH 2  --; and R 3  and R 4  are each independently selected from the group consisting of H, --CH 3 , --CH 2  CH 3 , --CH 2  OH, and --CH 2  --CH 2  --OH.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel derivatives oftris(p-hydroxyphenyl)ethane (THPE), to processes for preparing them, topolymer compositions which contain the novel compounds, and to the useof said compositions for a wide variety of end use applications.

2. Description of Related Art

The following prior art references are disclosed in accordance with theterms of 37 CFR 1.56, 1.97, and 1.98.

U.S. Pat. No. 3,579,542, issued May 18, 1971, to Meyer et al. discloses4,4',4"-trishydroxytriphenylmethymethane endowed with laxative(cathartic) properties.

U.S. Pat. No. 4,113,879, issued Sep. 12, 1978, to Jones et al.,discloses pharmaceutical compositions containing4,4'-dihydroxy-3,3'-triphenylmethanedicarboxylic acids.

U.S. Pat. No. 4,394,496, issued Jul. 19, 1983, to Paul G. Schraderdiscloses polyglycidyl ethers of tris(hydroxyphenyl) alkanes, theirblends with other epoxy compounds, and their cured products.

U.S. Pat. No. 4,695,408, issued Sep. 22, 1987, to Kuo Y. Chang,discloses processes for preparing tris(p-hydroxy-disubstitutedphenyl)methanes from 2,6-disubstituted phenols and salicylaldehyde.

U.S. Pat. No. 4,764,580, issued Aug. 16, 1988, to Martin et al.,discloses processes for preparing epoxy resins employing1,1,10-tri(hydroxyphenyl)-alkanes or -alkenes, as the phenolic reactant.

U.S. Pat. No. 4,992,598, issued Feb. 12, 1991, to Strutz, disclosesprocesses for the purification of 1,1,1,tris(4"-hydroxypheiiyl)ethane.

U.S. Pat. No. 5,130,467, issued Jul. 14, 1992, to Mott et al., disclosesnovel compositions of matter, which are mono-, di-, or tri-acrylateesters of 1,1,1-trishydroxyphenylethane and processes for preparing thesame.

All of the above-cited prior art patents are incorporated herein byreference in their entirety.

SUMMARY OF THE INVENTION

The present invention provides novel amine products ("NAP") endowed withchain extension activity for formulations such as polyureas and whichhave the general formula: ##STR2## wherein n is 0-1000; and R₁ and R₂are from the group --CH₂ --CH₂ --; --CH₂ --C(CH₃)H--; and --C(CH₃)H--CH₂--; and R₃ and R₄ are each independently selected from the groupconsisting of H, --CH₃, --CH₂ CH₃, --CH₂ OH, and --CH₂ CH₂ --OH.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention provides novel amine products (NAP) which arederivatives of tris(p-hydroxyphenyl)ethane (THPE), a well-known basicbuilding block for numerous organic compounds. These novel NAP's havethe general formula as follows: ##STR3## wherein: n is 0 to 1000(preferably 0 to 100);

R₁ equals R₂ ;

R₁ and R₂ represent a member from the group:

--CH₂ --CH₂ --

--CH₂ --C(CH₃)H--

--C(CH₃)H--CH₂ --

and R₃ and R₄ are each independently selected from the group:

H

--CH₃

--CH₂ CH₃

--CH₂ OH

--CH₂ --CH₂ --OH

The compounds having the general formula (I) can be prepared by reactingan alkali metal salt of tris(p-hydroxyphenyl)ethane (THPE) with an oxidematerial such as ethylene oxide or propylene oxide in the presence of asuitable catalyst to form the novel NAP having the above formula (I).This overall reaction scheme using ethylene oxide is shown as follows:##STR4##

In equation (A), M is an alkali metal such as potassium.

In equation (B), X represents the number of molar equivalents of theethylene oxide (or propylene oxide) used to form the chain, and n+1equals X. n can be 0 to 1000, but is preferably from 0 to 100.

In equation (C), HNR₁ R₂ is ammonia or a primary or secondary aminehaving the same groups (R₃ and R₄), as hereinbefore described in formula(1).

In the formulation of the alkali metal salt of THPE, equation (A), thereactants are mixed together in a reaction vessel along with a suitableinert solvent such as isopropanol and then heated at about 30° C. toabout 100° C. for a sufficient period of time until all the solids aredissolved into the liquid. The resultant reaction mass is then allowedto cool to room temperature and then the desired alkali metal salt isallowed to crystalize over a period of time suitable to promotecrystallization from the solution. The solid material, i.e. the THIPEsalt, is then separated from the mother liquor by any conventionalmeans, such as filtration. The solid material is then washed with asuitable inert solvent such as heptane and then dried at a temperatureof from about 30° C. to about 100° C., under vacuum, where so desired.

In conjunction with equation (B) above, the alkali metal salt of THPE ischarged into a reaction vessel along with preselected quantities ofeither ethylene oxide or propylene oxide and a suitable inert solventsuch as dimethylformamide (DMLF). The reaction vessel is provided with acondenser and a mechanical stirrer. The reaction mass is then slowlyheated from room temperature (i.e. 20° C.) to about 100° C. over aperiod of time to insure that the ethoxylation or propoxylation takesplace in the desired fashion. While this part of the process isconducted at atomospheric pressure, it is within the scope of thepresent invention to conduct this reaction under pressure, e.g. fromabout 20 psig to about 300 psig, and thus reduce the reaction times.After the reaction has taken place, the reaction mass is allowed to coolto room temperature and then a suitable de-salting agent, such as aceticacid, is added to this mass in order to remove and inactivate the alkalimetal ion. This ion complex precipitates and the resultant suspension isseparated from the mother liquor by any conventional means such asfiltration. This liquid is then reduced under vacuum to a solid materialwhich represents the ethoxylated or propoxylated TIHPE.

Referring to equation (C) above, the final novel amine product (NAP) isobtained by the reductive amination of the ethoxylated or propoxylatedTHPE material ("E/P THPE"). Specifically, this amine product (NAP) isprepared from E/P TBPE by contacting the E/P THPE with ammonia or aprimary or secondary amine ("amine") in the presence of a solvent, aco-catalyst, and an acid-promoted catalyst under conditions oftemperature and pressure which allow the full reductive amination of E/PTHPE to form NAP to occur. In this manner, NAP is produced in very highyields.

In the process of the instant invention, it is preferred that excessammonia or amine be used over that required to react with E/P T]HPE.Thus, it is preferred that E/P THPE and ammonia or amine be supplied ina molar ratio of from about 1:1 to about 1:10.

The term "acid-promoted" catalyst as used herein means a hydrogenationcatalyst such as Raney nickel, Raney cobalt, palladium on carbon, andplatinum on carbon.

It has also been discovered that the addition of a co-catalyst such asacetic acid and oxalic acid produces a marked improvement in the yieldof NAP in the process using this "acid-promoted" catalyst. It is notunderstood exactly why the yield is substantially increased by the useof this co-catalyst with the other catalyst, and the result isunexpected and surprising.

The amount of "acid-promoted" catalyst used is at least five (5) percentby weight, based on the weight of the E/P TBPE supplied. Preferably, thecatalyst present is from about ten (10) percent to about thirty (30)percent by weight, based on the weight of the E/P THPE.

The acid-promoted catalyst can be in any form; e.g. lumps, filaments,tablets, pellets, granules, etc. It can also be used in crushed form oras a powder. The grains should be neither too fine nor too coarse.Coarse catalyst particles are undesirable because they have too small asurface area to adequately catalyze the reaction. On the other hand,fine-grained catalysts, although highly reactive due to their largesurface area, are separated only with great difficulty by sedimentation,centrifugation, or filtration. The person of ordinary skill will knowhow to properly select the catalyst particle size.

The amount of co-catalyst used is at least one (1) percent by weight,based on the weight of the E/P TBPE supplied. Preferably, theco-catalyst present is from about one (1) percent to about ten (10)percent by weight, based on the weight of the E/P THPE.

Before the reaction begins, the hydrogenation catalyst is suspended in asolvent. This solvent should be inert to the reaction taking place; i.e.it must not interfere with the hydrogenation. Suitable solvents are thereaction product itself; aliphatic, cycloaliphatic, aromatichydrocarbons, ether, alcohols, and mixtures thereof. In many cases,cyclic ethers and/or aliphatic alcohols have particularly proven theirworth. Solvents include polar liquids which can be used in accordancewith the instant invention which include lower alkanols includingcycloalkanols, e.g., those having from one (1) to eight (8) carbonatoms, such as methanol, ethanol, isopropanol, butanol, pentanol,cyclohexanol, and cyclobutanol, as well as polar asymmetricallyhalogenated hydrocarbons, e.g., those having from one (1) to eight (8)carbon atoms, such as chloroform, trifluorotrichloroethane, andtrichlorofluoromethane, and mixtures of the above. Aliphatic alcoholshaving from one (1) to six (6) carbon atoms are desirable. Methanol,ethanol, propanol, i-propanol, n-butanol, and/or i-butanol have provenparticularly successful. In view of their good solubility in water,methanol, ethanol, and/or propanols are strongly recommended. Methanoland/or ethanol and/or isopropanol have been found to be most suitable.

In preferred embodiments of the equation (C) above, the acid-promotedcatalyst is charged into a suitable reaction vessel capable of beingheated under pressure, such as an autoclave. The air in the reactionvessel is displaced, preferably by sweeping out the air with nitrogen,followed by hydrogen, after the reaction vessel is charged with asolvent. The reaction vessel is sealed, and the vessel and contents arethen heated by any suitable means to a reaction temperature sufficientto promote full reductive amination of the E/P TBPE in the presence ofthe acid-promoted catalyst and hydrogen. When the reaction temperatureis reached, E/P THPE, a co-catalyst, hydrogen and ammonia or amine areintroduced into the autoclave to pressurize the reaction vessel andprovide feed materials thereto. The reaction is continued, agitating thecontents at the elevated reaction temperature and supplying additionalhydrogen and ammonia or amine as needed to maintain the desired pressurewithin the reaction vessel until no further NAP is formed and the E/PTHPE is consumed. The reaction is usually complete in 3 to 20 hours.

The reaction is closely followed by removing samples periodically fromthe reaction vessel and analyzing the products by liquid chromatography.Further evidence that the reaction is complete is indicated by a statichydrogen pressure within the reaction vessel.

After the reaction has been determined to be complete, the reactionmixture is permitted to cool, the reaction vessel is opened, and thecontents are discharged. At this point, the contents consist essentiallyof the acid-promoted catalyst and a solvent solution of NAP. The solventsolution of NAP is separated from the catalyst by any suitable means,such as by filtration or decantation. The NAP is recovered by reducingto a solid under vacuum.

In the past, alcoholic slurries of Raney metal catalysts having requiredspecial handling, as they are well known as being pyrophoric. If allowedto dry in air, a Raney metal catalyst will flare rapidly to red heat andprovide an ignition source for exposed combustibles. This has presenteda particular problem when charging batch reactors with such catalystsand when removing the product. Surprisingly, the acid-promoted Raneymetal catalysts useful in this invention have been found to benon-pyrophoric. This property is unique and eliminates one of the chiefhazards in the manufacture of amines by reductive amination.

In another embodiment of equation (C) above, the reaction solution isprepared by mixing said catalyst in a solvent such as isopropanol. Thenthe E/P THPE and co-catalyst are fed into the reaction vessel.Generally, the concentration of E/P THPE will vary from about thirty(30) to sixty (60) percent (weight basis) based upon the total weight ofthe reaction solution. Ammonia or amine is preferably added in an amountof from 3 to 15 moles of ammonia or amine for every mole of E/P THPEused. Ammonia or amine in excess of the stoichiometric amount isgenerally required. The solvent is present as an inert diluent and theamount of solvent can vary widely, but should not be used in an amountwhich would greatly increase recovery costs. It will be understood bythose skilled in the art that the actual amounts of reactants used inthis process will vary widely, depending upon the size of the equipmentused in commercial production.

The reaction temperature for the reductive amination is preferably atleast 150° C., preferably 175° C. to 350° C., and more preferably 200°C. to about 300° C. Within this range, excellent yields and reactionrates are obtained. Reaction temperatures much below 100° C. reduce thereaction rates and full reductive amination does not occur. The upperlimit of reaction temperatures is dependent upon the equipmentlimitations.

When the reaction temperature is reached, hydrogen (in addition toammonia or amine), is introduced into the autoclave to pressurize thereaction vessel to a total pressure preferably of at least 500 psi.Generally, the total pressure will be from 500 to 10,000 psi, preferablyfrom about 2000 psi to about 3000 psi, as within this range, excellentyields and reaction rates are achieved. Pressures much below 500 psireduce the reaction rates and full reductive amination does not occur.The upper pressure at which the process can be operated is limited onlyby the structural limitations of the equipment used.

It is also within the scope of the present invention to employ otherreductive amination procedures disclosed in the art. One such procedureis described in U.S. Pat. No. 4,766,245 which is incorporated herein byreference in its entirety.

The NAP of this invention are particularly suited for reaction withisocyanates to manufacture articles by a Reaction Injection Molding(RIM) process.

RIM is a technique for the rapid mixture and molding of large,fast-curing urethane parts. RIM polyurethane parts are used in a varietyof exterior body applications on automobiles where the light weightcontributes to energy conservation. RIM parts are generally made byrapidly mixing active hydrogen-containing materials with polyisocyanateand placing the mixture into a mold where reaction proceeds. Afterreaction and de-molding, the parts may be subjected to an additionalcuring step which comprises placing the parts in an oven, held at 250°F. or higher.

Surprisingly, it also has been found that the NAP of this invention areuseful as curing agents in forming clear epoxy castings and adhesiveswith highly satisfactory physical properties. Such epoxy products findapplication in the electrical and electronic fields. These NAP also havebeen found to be suitable for use in polyamides, polyimides, and epoxyresins.

The following specific examples are supplied for the purpose of betterillustrating the invention. These examples are not intended, however, tolimit or restrict the scope of the invention in any way and should notbe construed as providing conditions, parameters, or values which mustbe utilized exclusively in order to practice the present invention.

EXAMPLE 1 Synthesis of Potassium Salt of Tris(p-Hydroxyphenyl)Ethane(THPE)

A mixture of tris(p-hydroxyphenyl)ethane (THPE) (309 g), potassiumhydroxide (120 g), and isopropanol (3 L) is charged to a 5 L glassreactor fitted with a condenser and mechanical stiffer. The mixture isheated until all of the solids are dissolved (85° C.). The solution isthen cooled to room temperature and the product is allowed tocrystallize for 10 hours. The solid is isolated by filtration, washedwith heptane (1 L), and dried under vacuum (60 torr., 50° C.). Theproduct is an off-white solid and weighs 295 g (80%). This reaction isrepresentative of equation (A) above.

EXAMPLE 2

A mixture consisting of (Example 1) product (151 g), propylene oxide(342 g), and DNW (900 mL) is charged to a 3 L glass reactor fitted witha condenser and mechanical stirrer. The reaction is heated and thetemperature slowly increases from 52° C. to 82° C. over a period of 3hours. The mixture is cooled to room temperature and acetic acid (73 g)is slowly added. The suspension is filtered and the filtrate is reducedunder vacuum to provide a solid. The solid product is a white materialand weighs 74 g (81%). Typical physical properties are given in Table 1.This reaction is representative of equation (B) above, except thatpropylene oxide is used instead of ethylene oxide.

                  TABLE I                                                         ______________________________________                                        Typical Properties of Propoxylated                                            Tris(p-Hydroxyphenyl)Ethane (THPE)                                                          Propoxylated                                                    Property      Tri(p-Hydroxyphenyl)Ethane (THPE)                               ______________________________________                                        Average n     (wt %)                                                          n = 0         15.6                                                            n = 1         60.1                                                            n = 2         24.3                                                            n = 3         --                                                              Molecular Weight                                                                            663.2                                                           (Average)                                                                     Melting Point 105-121° C.                                              Density (@ 27° C.)                                                                   1.09 g/mL                                                       Color         White                                                           Solubility (>5 wt %)                                                          Water         No                                                              Acetone       Yes                                                             Methanol      Yes                                                             N,N-Dimethylformamide                                                                       Yes                                                             Heptane       No                                                              Ethyl Acetate Yes                                                             ______________________________________                                    

EXAMPLE 3

In a 1 liter autoclave, a solution of propoxylated THPE (100 g, 0.66moles), and glacial acetic acid (5.0 g, 0.08 moles) in isopropanol (300g, 4.0 moles), and Raney Nickel catalyst (10.0 g) were charged. Thereactor is purged 3 times with nitrogen (100 psi) and then evacuated toapproximately 30 torr. Then anhydrous ammonia (219 g, 12.0 moles) ischarged while maintaining the reactor temperature below 30° C., Thereactor is heated and maintained at 220° C. for 1.5 hours. Hydrogen isthen charged to a pressure of 2500 psi. The temperature is maintained at220° C. for 2 hours at a constant hydrogen pressure of 2500 psi. Thereactor is cooled to 40° C. and then discharged. The ammonia is removedunder vacuum and the product reduced to a solid under vacuum and weighed(80.1 g, 0.54 moles, 80%). The product is an off-white material. Thisreaction is representative of equation (C) above, except that the TBPEderivative used is propoxylated instead of ethoxylated.

EXAMPLE 4 Different Catalyst Without Acetic Acid

In a I liter autoclave, a solution of propoxylated THPE (100 g, 0.66moles) in isopropanol (300 g, 40 moles), and palladium on carboncatalyst (50% H₂₀) (20 g) were charged. The reactor is purged 3 timeswith nitrogen (100 psi) and then evacuated to approximately 30 torr.Then anhydrous ammonia (219 g, 12 moles) is charged while maintainingthe reactor temperature below 30° C. The reactor is heated andmaintained at 221° C. for 1.5 hours. Hydrogen is then charged to apressure of 2500 psi. The temperature is maintained at 221° C. for 2hours at a constant hydrogen pressure of 2500 psi. The reactor is cooledto 40° C. and then discharged. The ammonia is removed under vacuum andthe product reduced to a solid under vacuum and weighs (80.3 g, 0.54moles, 81%). This reaction is representative of equation (C) above,except that the THPE derivative used is propoxylated instead ofethoxylated.

EXAMPLES 5-20

Using the procedures set forth in Examples 1-4 above, the compoundsreported in Table II are obtained.

                                      TABLE II                                    __________________________________________________________________________     ##STR5##                                                                     Example                                                                            R.sub.1 /R.sub.2                                                                        n (Average)                                                                          R.sub.3   R.sub.4                                       __________________________________________________________________________     5   CH.sub.2 CH.sub.2                                                                       2      H         H                                              6   CH.sub.2 CH.sub.2                                                                       12     H         H                                              7   CH.sub.2 CH.sub.2                                                                       84     H         H                                              8   CH.sub.2 CH.sub.2                                                                       4      CH.sub.3  CH.sub.3                                       9   CH.sub.2 CH.sub.2                                                                       3      CH.sub.2 CH.sub.3                                                                       CH.sub.2 CH.sub.3                             10   CH.sub.2 CH.sub.2                                                                       3      CH.sub.2 OH                                                                             CH.sub.2 OH                                   11   CH.sub.2 CH.sub.2                                                                       3      CH.sub.2 CH.sub.3                                                                       CH.sub.2 OH                                   12   CH.sub.2 CH.sub.3                                                                       4      CH.sub. 2 CH.sub.2 OH                                                                   CH.sub.2 CH.sub.2 OH                          13   CH.sub.2 C(CH.sub.3)H                                                                   5      H         H                                             14   CH.sub.2 C(CH.sub.3)H                                                                   5      CH.sub.3  CH.sub.3                                      15   CH.sub.2 C(CH.sub.3)H                                                                   5      CH.sub.2 CH.sub.3                                                                       CH.sub.2 CH.sub.3                             16   CH.sub.2 OC(CH.sub.3)H                                                                  2      CH.sub.2 OH                                                                             CH.sub.2 OH                                   17   CH.sub.2 C(CH.sub.3)H                                                                   5      CH.sub.2 CH.sub.3                                                                       CH.sub.2 OH                                   18   CH.sub.2 C(CH.sub.3)H                                                                   5      CH.sub.2 CH.sub.2 OH                                                                    CH.sub.2 CH.sub.2 OH                          19   C(CH.sub.3)HCH.sub.2                                                                    3      H         CH.sub.3                                      20   C(CH.sub.3)HCH.sub.2                                                                    3      H         CH.sub.2 OH                                   __________________________________________________________________________

EXAMPLE 21 Synthesis of a Polyurea with NAP

A 2.0 g sample (0.012 mole) of tolylenediisocyanate (a 80:20 mixture of2,4 and 2,6 tolylenediisocyante) is mixed carefully with a 2.9 g sample(0.012 mole) of the amino product, prepared according to the procedurein Example 3 above. The mixture thickens and hardens to a glassy resinwith the generation of heat. The material is a hard, clear, amber solidand is found suitable for use in automobile parts.

EXAMPLES 22-38 Preparation of Polyurethanes Containing NAP

Polyurethanes are prepared incorporating NAP by substitution of NAP forother polyols present in a reaction mixture. Examples are described inthe Encyclopedia of Polymer Science & Engineering, Volume 1, pgs.243-303 (2nd Edition, 1988, Wiley). As used herein, the term,"polyurethane" refers to materials that include the carbamate functionas well as other functional groups such as ester, ether, amide, andurea. Polyurethanes are usually produced by the reaction of apolyfunctional isocyanate with a polyol or other hydroxyl-containingreactant. Since the functionality of the hydroxyl-containing reactant orthe isocyanate can be adjusted, a wide variety of branched orcross-linked polymers can be formed. The hydroxyl-containing componentmay be of a wide variety of branched or cross-linked polymers can beformed. The hydroxyl-containing component may be of a wide variety ofmolecular weights and types including polyester and polyester polyols.The polyfunctional isocyanates may be aromatic, aliphatic,cycloaliphatic, or polycyclic in structure and can be used directly asproduced or modified. The flexibility in reactants leads to the widerange of physical properties of available materials. Present inventionpolymers are prepared by substituting NAP for a portion of thehydroxyl-containing reactant in a mole ratio of NAIP/hydroxyl from about0.001:1 to about 1:1 for the polyol in a polyurethane reaction mixtureor, in other words, from about 0.05 to about 50 mole percent of thetotal mixture as described above in connection with Example 21.Specifically, Example 21 is repeated using the NAP compounds fromExamples 10, 11, 12, 16, 17, 18, and 20. The resultant polyurethanecompositions are found functional in a wide variety of automobile parts.

The NAP are also found useful when incorporated into polyamides,polyimides, epoxy resins, and polyureas, in addition to thepolyurethanes.

What is claimed is:
 1. Amino compounds having the structural formula(1): ##STR6## wherein n is 0-1000; and R₁ =R₂, and R₁ and R₂ are fromthe group --CH₂ --CH₂ --; --CH₂ --C(CH₃)H--; and --C(CH₃)H--CH₂ --; andR₃ and R₄ are each independently selected from the group consisting ofH, --CH₃, --CH₂ CH₃ ; --CH₂ OH; and --CH₂ --CH₂ -OH.
 2. Amino compoundshaving the structural formula (II): ##STR7## wherein n is 0-1000; and R₁and R₂ are each independently selected from the group consisting of H,--CH₃, --CH₂ CH₃, --CH₂ OH; and --CH₂ --CH₂ --OH.
 3. Amino compoundshaving the structural formula (111): ##STR8## wherein n is 0-1000; andR₁ and R₂ are each independently selected from the group consisting ofH, --CH₃, --CH₂ CH₃, --CH₂ OH; and --CH₂ --CH₂ --OH.
 4. Amino compoundshaving the structural formula (IV): ##STR9## wherein n is 0-1000; and R₁and R₂ are each independently selected from the group consisting of H,--CH₃, --CH₂ CH₃, --CH₂ OH; and --CH₂ --CH₂ --OH.